EP1293496A2 - Procédé pour la préparation des amines - Google Patents
Procédé pour la préparation des amines Download PDFInfo
- Publication number
- EP1293496A2 EP1293496A2 EP02020470A EP02020470A EP1293496A2 EP 1293496 A2 EP1293496 A2 EP 1293496A2 EP 02020470 A EP02020470 A EP 02020470A EP 02020470 A EP02020470 A EP 02020470A EP 1293496 A2 EP1293496 A2 EP 1293496A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- raney
- acid
- catalyst
- mixtures
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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- 238000000034 method Methods 0.000 title claims abstract description 26
- 150000001412 amines Chemical class 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 150000001728 carbonyl compounds Chemical class 0.000 claims abstract description 21
- 238000005576 amination reaction Methods 0.000 claims abstract description 20
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 19
- 150000002367 halogens Chemical class 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 150000001298 alcohols Chemical class 0.000 claims abstract description 12
- 229910017464 nitrogen compound Inorganic materials 0.000 claims abstract description 7
- 150000002830 nitrogen compounds Chemical class 0.000 claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- 230000002378 acidificating effect Effects 0.000 claims description 17
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 150000003863 ammonium salts Chemical class 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical class CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 5
- PJGSXYOJTGTZAV-UHFFFAOYSA-N pinacolone Chemical compound CC(=O)C(C)(C)C PJGSXYOJTGTZAV-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Chemical class CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Chemical class OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 235000005985 organic acids Nutrition 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical class COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical class OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 229910017061 Fe Co Inorganic materials 0.000 claims description 2
- 229910003271 Ni-Fe Inorganic materials 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical class O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims 1
- 125000003710 aryl alkyl group Chemical group 0.000 abstract description 3
- 239000011973 solid acid Substances 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229910000564 Raney nickel Inorganic materials 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- -1 phenyl radicals Chemical class 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000007868 Raney catalyst Substances 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- JZBVVNOPMZSANQ-UHFFFAOYSA-N 3,3-dimethylbutan-2-one Chemical compound CC(=O)C(C)(C)C.CC(=O)C(C)(C)C JZBVVNOPMZSANQ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910020630 Co Ni Inorganic materials 0.000 description 2
- 229910002440 Co–Ni Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000004045 organic chlorine compounds Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 150000003139 primary aliphatic amines Chemical class 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000009419 refurbishment Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000005619 secondary aliphatic amines Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
- C07C209/26—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with hydrogen
Definitions
- the invention relates to a process for the preparation of amines by catalytic hydrogenating amination of carbonyl compounds or alcohols, the halogen-containing Contain impurities.
- the hydrogenating amination of carbonyl compounds with ammonia or primary or secondary amines is a standard process for the production of amines.
- the reaction is usually carried out in the presence of metallic catalysts, for example Raney-Ni, Raney-Co, Pt / activated carbon, Pd / activated carbon, Pd / BaSO 4 , Rh / Al 2 O 3 being used as catalysts.
- metallic catalysts for example Raney-Ni, Raney-Co, Pt / activated carbon, Pd / activated carbon, Pd / BaSO 4 , Rh / Al 2 O 3 being used as catalysts.
- the carbonyl compound to be aminated contains significant amounts of chlorine due to the manufacturing process (for example> 50 ppm), this leads to problems in the hydrogenating amination. So result, for example, in lower selectivities and space-time yields and one premature deactivation or destruction of the catalyst. In many cases, only one Partial sales can be achieved, which makes processing difficult. In particular, fixed bed hydrations are in the presence of halogens or halogen-containing impurities not economically feasible due to the disintegration of the catalyst.
- DE-A-100 53 380 which is older and not pre-published, relates to a method for Production of amines by catalytic hydrogenative amination of carbonyl compounds or alcohols which have at least one aromatic substituted by halogen Have core that is not changed in the hydrogenating amination.
- the Hydrogenation is in the presence of Co- and / or Ni-containing catalysts and solid acidic cocatalysts and in the absence of organic sulfur compounds carried out.
- the object of the present invention is to provide a method for simple and inexpensive production of amines by hydrogenating amination corresponding carbonyl compounds or alcohols that have a significant content of Halogen (at least 50 ppm, in particular organically bound), and that with high space-time yields with low catalyst consumption to the desired Products.
- the Co- and / or Ni-containing catalysts are preferably selected from Raney-Co, Raney-Ni, Raney-Co-Ni, Raney-Ni-Fe, Raney-Ni-Fe-Co, Ni-Co, Ni / Co mixed oxides or Mixtures of these, which can also be present on inorganic supports.
- the Co and / or Ni catalysts can additionally 0 to 80 wt .-% Cu and 0 contain up to 10 wt .-%, preferably 0 to 5 wt .-% of other metals, calculated as Metal and based on the total weight of the catalyst.
- the Co- and / or Ni-containing catalysts are preferably supported in the form of elemental Co- and / or Ni sponge, Raney cobalt or Raney nickel, Co or Ni or Co-oxide or Ni-oxide (Supported catalysts) used. They can also be mixed in any weight ratio. Carriers for this are, for example, Al 2 O 3 , SiO 2 , TiO 2 , ZrO 2 , activated carbon and other catalyst supports known to the person skilled in the art.
- Raney catalysts such as Raney cobalt, Raney-Cobalt-Nickel, Raney-Cobalt-Nickel-Iron, Raney-Cobalt-Nickel-Iron-Chrome or Raney cobalt or Raney nickel with doping of other transition metals in anhydrous or water-moist or solvent-moist form used.
- Raney cobalt which is in each case 0 or 0.1 to 10; preferably up to 5 Wt .-% Al, Ni, Fe, Cr contains used.
- the Co or Ni-containing catalyst is in an amount of 0.01 to 20 wt .-%, preferably 0.1 to 10 wt .-% and particularly preferably 0.3 to 5% by weight, based on the carbonyl compound to be aminated, used.
- a Ni or Co-Ni catalyst can also preferably be used which is supported on ZrO 2 and contains 0 to 50% by weight of CuO, calculated as CuO and based on the total weight of the catalyst.
- the solid acidic cocatalysts are preferably selected from Metal oxides or mixed metal oxides, zeolites, metal or ammonium salts of Mineral acids or organic acids, acidic ion exchangers or mixtures thereof.
- Preferred solid acid contacts in the process according to the invention are metal oxides, such as oxides or mixed oxides of the elements Zr, Ti, Cr, Mo, W, Mn, Fe, B, Al, Si, zeolites of natural and synthetic origin, metal or ammonium salts of strong mineral acids such as Hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and strong organic acids such as formic acid, acetic acid, propionic acid and sulfonic acid, acidic ion exchangers such as Nafion etc. are used.
- ZrO 2 is used.
- the amounts of acid contacts used are preferably between 0.1 and 20% by weight, preferably between 1-10% by weight, based on the carbonyl compound to be aminated.
- the support materials such as Al 2 O 3 , SiO 2 , TiO 2 , ZrO 2 etc. can function as acidic contacts. In this case, the addition of an additional acidic contact is not necessary. If the ammonium salts are used as acid contacts, the conventional acid can be used directly instead of the ammonium salts. The ammonium salts then form through the reaction of the acid with ammonia or amines.
- Metal oxides or mixtures thereof are preferably used as acid contacts in the process according to the invention.
- ZrO 2 is particularly preferred.
- the hydrogenating amination can be carried out in the suspension or fixed bed mode become.
- the carbonyl compounds or alcohols used according to the invention can largely freely chosen.
- the aryl radicals are particularly preferably phenyl radicals and the aralkyl radicals are benzyl radicals.
- the alkyl radicals are preferably C 1-6 alkyl radicals, the cycloalkyl radicals are C 3-6 cycloalkyl radicals.
- none of the radicals hydrogen is particularly preferred.
- the carbonyl compound is pinacolone or a derivative thereof.
- the carbonyl compounds or alcohols to be aminated used according to the invention contain at least 50 ppm, particularly preferably 50 ppm to 10 wt .-%, in particular 100 ppm to 10% by weight of halogen.
- the quantities given relate to Mixture of the carbonyl compounds or alcohols and the halogen or halogen-containing compounds.
- halogen and the quantity halogen atoms present in the mixture, which are bound in chemical form or can be present as ions or salts.
- it is organic bonded halogen, that is organic compounds, the halogen atoms, in particular Contain chlorine atoms, chemically bound.
- the quantities refer to the halogen itself regardless of the type and size of the organic residue.
- the halogen is present as an ionic impurity or in particular bound organic impurities in the carbonyl compound used.
- the mixture used according to the invention is therefore in particular Pinacolone or its derivatives contaminated with organic chlorine compounds.
- the nitrogen compound of the formula (IV) is preferably ammonia or primary or secondary aliphatic amines.
- the latter preferably have C 1-6 alkyl radicals.
- Ammonia is particularly preferably used as the nitrogen compound.
- the amination in the process according to the invention can be carried out in solvents, for example Alcohols such as methanol, ethanol, propanol, butanol, aliphatic or aromatic Hydrocarbons such as toluene, xylene, cyclohexane, isooctane, ethers such as tetrahydrofuran, Dioxane, methyl tert-butyl ether can be carried out.
- solvents for example Alcohols such as methanol, ethanol, propanol, butanol, aliphatic or aromatic Hydrocarbons such as toluene, xylene, cyclohexane, isooctane, ethers such as tetrahydrofuran, Dioxane, methyl tert-butyl ether can be carried out.
- solvents for example Alcohols such as methanol, ethanol, propanol, butanol, aliphatic or aromatic Hydrocarbons such
- the amination is preferably at a temperature of 10 to 250 ° C, preferably from 40 to 150 ° C and at a pressure of 10 to 200 bar, preferably from 30 to 130 bar carried out.
- the process according to the invention can be carried out in a fixed bed, but also e.g. in an autoclave in suspension as described below.
- the containing Co or Ni and the acidic cocatalysts and the carbonyl compound are under Shielding gas is introduced into the reactor in any order.
- Ammonia or amines are metered in with stirring.
- the mixture is on Reaction temperature heated, and then hydrogen is at reaction pressure pressed.
- the reactor is turned on Cooled to room temperature, relaxed and emptied.
- the catalysts are filtered off and used again for the next reaction cycle. Working up the The reaction product then takes place in a manner known to the person skilled in the art.
- the process can be carried out batchwise, for example in an autoclave, such as also continuously, for example in a pressure pipe with a connected separator and depressurization.
- the catalysts, pinacolone (Cl content (org. Bound): 280 ppm) and methanol as the solvent are placed in a 2.5 l autoclave which has been flushed with nitrogen and filled with a disk stirrer and two wave breakers. At room temperature, ammonia and then hydrogen are first injected to 20 bar with stirring (500 rpm). The mixture is heated to the reaction temperature, pressed to reaction pressure with hydrogen and then stirred under constant hydrogen pressure. After the hydrogen uptake has ended, the autoclave is cooled, expanded, degassed and emptied. The compositions of the reaction products are determined by gas chromatography. The test results are summarized in Table 1.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10145119 | 2001-09-13 | ||
| DE10145119A DE10145119A1 (de) | 2001-09-13 | 2001-09-13 | Verfahren zur Herstellung von Aminen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1293496A2 true EP1293496A2 (fr) | 2003-03-19 |
| EP1293496A3 EP1293496A3 (fr) | 2003-06-25 |
Family
ID=7698895
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP02020470A Withdrawn EP1293496A3 (fr) | 2001-09-13 | 2002-09-12 | Procédé pour la préparation des amines |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US6689914B2 (fr) |
| EP (1) | EP1293496A3 (fr) |
| JP (1) | JP4383726B2 (fr) |
| DE (1) | DE10145119A1 (fr) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8450530B2 (en) * | 2010-04-07 | 2013-05-28 | Basf Se | Process for preparing unsymmetric secondary tert-butylamines in the gas phase |
| JP6948952B2 (ja) * | 2015-05-28 | 2021-10-13 | ビーエイエスエフ・ソシエタス・エウロパエアＢａｓｆ Ｓｅ | 均一系触媒によるカルボニル化合物の還元的アミノ化法 |
| CN111116377B (zh) * | 2019-12-16 | 2021-03-30 | 中国科学院大连化学物理研究所 | 一种制备己二胺的方法 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4152353A (en) | 1977-08-29 | 1979-05-01 | The Dow Chemical Company | Method of producing amines from alcohols, aldehydes, ketones and mixtures thereof |
| US5011996A (en) | 1988-07-20 | 1991-04-30 | Bayer Aktiengesellschaft | Process for the preparation of amines |
| US5530127A (en) | 1994-08-08 | 1996-06-25 | Basf Aktiengesellschaft | Preparation of amines |
| US20010003137A1 (en) | 1999-12-06 | 2001-06-07 | Jan Nouwen | Process for preparing monoisopropylamine |
Family Cites Families (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4123462A (en) * | 1976-01-07 | 1978-10-31 | Union Carbide Corporation | Amination process using nickel-rhenium catalysts |
| EP0017651A1 (fr) * | 1977-08-29 | 1980-10-29 | The Dow Chemical Company | Procédé pour la préparation d'amines à partir d'alcools, d'aldéhydes, de cétones ou de leurs mélanges, et le catalyseur utilisé |
| US4153581A (en) * | 1977-09-01 | 1979-05-08 | The Dow Chemical Company | Method of producing amines from alcohols, aldehydes, ketones and mixtures thereof |
| JPS5912106B2 (ja) * | 1979-02-21 | 1984-03-21 | 花王株式会社 | 脂肪族アミンの製造方法 |
| US4863890A (en) * | 1983-09-09 | 1989-09-05 | Berol Kemi Ab | Process for preparing a ruthenium-promoted, halogen-containing nickel and/or cobalt catalyst and a catalyst prepared by the process |
| SE461095B (sv) * | 1983-09-09 | 1990-01-08 | Berol Kemi Ab | Amineringsfoerfarande med anvaendning av en ruteniumdopad nickel och/eller kovoltkatalysator |
| US4625030A (en) * | 1984-05-23 | 1986-11-25 | Union Carbide Corporation | Potentiated nickel catalysts for amination |
| JPS6115865A (ja) * | 1984-06-29 | 1986-01-23 | Kao Corp | 第３級アミンの製造方法 |
| GB8707304D0 (en) * | 1987-03-26 | 1987-04-29 | Bp Chem Int Ltd | Chemical process |
| US5266730A (en) * | 1987-10-16 | 1993-11-30 | Kao Corporation | Process for preparing N-substituted amine |
| EP0489722B1 (fr) * | 1987-10-16 | 1995-02-01 | Kao Corporation | Procédé pour la préparation d'amine N-substituée |
| DE3741726A1 (de) * | 1987-12-09 | 1989-06-22 | Ruhrchemie Ag | Verfahren zur herstellung von tertiaeren n,n-dimethylaminen |
| DE3903367A1 (de) * | 1989-02-04 | 1990-08-16 | Basf Ag | Katalysator und verfahren zur hydrierenden aminierung von alkoholen |
| US5331101A (en) * | 1990-01-05 | 1994-07-19 | The Dow Chemical Company | Process for preparation of amines from alcohols, aldehydes or ketones |
| DE4010254A1 (de) * | 1990-03-30 | 1991-10-02 | Basf Ag | Verfahren zur herstellung von 2-(3-aminopropyl)-cycloalkylaminen |
| DE4010227A1 (de) * | 1990-03-30 | 1991-10-02 | Basf Ag | Verfahren zur herstellung von 3-aminomethyl-3,5,5-trimethyl-cyclohexylamin |
| US5430187A (en) * | 1991-12-21 | 1995-07-04 | Akzo N.V. | Method for manufacturing dibenzylamine |
| CA2115024A1 (fr) * | 1993-04-27 | 1994-10-28 | Atsushi Furutani | Procede de production d'amines |
| US5600000A (en) * | 1993-12-22 | 1997-02-04 | Union Carbide Chemicals & Plastics Technology Corporation | Reductive amination processes for the selective production of amino-ethylethanolamine |
| DE4343890A1 (de) * | 1993-12-22 | 1995-06-29 | Degussa | Verfahren zur Herstellung von 3-Aminomethyl-3,5,5-trimethylcyclohexylamin |
| DE19627265A1 (de) * | 1996-07-06 | 1998-01-08 | Degussa | Verfahren zur Herstellung primärer und/oder sekundärer Amine aus Oxoverbindungen |
| DE19812054A1 (de) * | 1998-03-19 | 1999-09-23 | Hoechst Schering Agrevo Gmbh | Verfahren zur Herstellung 4-substituierter cis-Cyclohexylamine |
| US5986141A (en) * | 1998-09-29 | 1999-11-16 | Eastman Chemical Company | Process for the production of cyclopropanemethylamine |
| DE19859776B4 (de) * | 1998-12-23 | 2008-06-19 | Basf Se | Verfahren zur Herstellung von Aminen |
| ATE272605T1 (de) * | 1999-12-06 | 2004-08-15 | Basf Ag | Verfahren zur herstellung von aminen |
| DE10053380A1 (de) | 2000-10-27 | 2002-05-08 | Basf Ag | Verfahren zur Herstellung von Aminen |
-
2001
- 2001-09-13 DE DE10145119A patent/DE10145119A1/de not_active Withdrawn
-
2002
- 2002-09-05 US US10/234,170 patent/US6689914B2/en not_active Expired - Fee Related
- 2002-09-11 JP JP2002265909A patent/JP4383726B2/ja not_active Expired - Fee Related
- 2002-09-12 EP EP02020470A patent/EP1293496A3/fr not_active Withdrawn
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4152353A (en) | 1977-08-29 | 1979-05-01 | The Dow Chemical Company | Method of producing amines from alcohols, aldehydes, ketones and mixtures thereof |
| US5011996A (en) | 1988-07-20 | 1991-04-30 | Bayer Aktiengesellschaft | Process for the preparation of amines |
| US5530127A (en) | 1994-08-08 | 1996-06-25 | Basf Aktiengesellschaft | Preparation of amines |
| US20010003137A1 (en) | 1999-12-06 | 2001-06-07 | Jan Nouwen | Process for preparing monoisopropylamine |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4383726B2 (ja) | 2009-12-16 |
| EP1293496A3 (fr) | 2003-06-25 |
| US20030097021A1 (en) | 2003-05-22 |
| DE10145119A1 (de) | 2003-04-03 |
| US6689914B2 (en) | 2004-02-10 |
| JP2003137845A (ja) | 2003-05-14 |
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